For most applications, heterostructures in nanowires (NWs) with lattice mismatched materials are required and promise certain advantages thanks to lateral strain relaxation. The formation of Si/Ge axial heterojunctions is a challenging task to obtain straight, defect free and extended NWs. And the control of the interface will determine the future device properties. This paper reports the growth and analysis of NWs consisting of an axial Si/Ge heterostructure grown by a vapor-liquid-solid process. The composition gradient and the strain distribution at the heterointerface were measured by advanced quantitative electron microscopy methods with a resolution at the nanometer scale. The transition from pure Ge to pure Si shows an exponential slope with a transition width of 21 nm for a NW diameter of 31 nm. Although diffuse, the heterointerface makes possible strain engineering along the axis of the NW. The interface is dislocation-free and a tensile out-of-plane strain is noticeable in the Ge section of the NW, indicating a lattice accommodation. Experimental results were compared to finite element calculations.